Dry-cleaning composition and process



United rates Patent Office 3,057,676 Patented Oct. 9, 1962 3,057,676 DRY-CLEANING CtEMPOSETHUN AND PROCESS Hans Wedell, Dusseldorf-Holthausen, Germany, assignor to Bohrne Fettchemie G.m.b.H., Dusseldorf, Germany, a corporation of Germany No Drawing. Filed Apr. 22, 1958, Ser. No. 730,049 Claims priority, application Germany Apr. 27, 1957 20 Claims. (til. 8-142) This invention relates to a method and a bath composition for dry-cleaning of textiles, feathers, fillers or like materials. It more particularly relates to a drycleaning method and bath modified with high molecular weight amine compounds as dispersing agents.

It is known that the degree of effectiveness of drycleaning baths can be improved by the addition of surface-active substances which are commonly referred to as cleansing intensifiers. For this purpose the cationic quaternary ammonium compounds have been used in addition to non-ionic and anionic materials.

In dry-cleaning practice it has further been found advantageous to add small amounts of water to the drycleaning baths; for example, to facilitate the removal of sugar-containing and other water-soluble soil. The surface-active substances added to the dry-cleaning baths not only improve the cleansing action but also have the purpose of dispersing the necessary water in the cleansing bath to form a stable dispersion. In this connection, the satisfactory filterability of the dry-cleaning bath must be given special consideration. It has been found that some of the known additives considerably increase the filter pressure while the formation of the dispersion is improved only to a minor degree.

It is an object of this invention to provide a dry-cleaning method and bath which are also effective in removing water-soluble soil.

A further object is to provide a dry-cleaning bath comprising a stable dispersion of an organic dry-cleaning agent and water.

Another object is to provide a dispersing agent for use in preparing dry-cleaning baths containing an organic cleaning agent and water.

Another object is to provide a dry-cleaning bath containing a dry-cleaning agent and water which has improved dispersion stability without decrease in filterability.

These and other objects of my invention will become apparent as the description thereof proceeds.

I have now found that dry-cleaning baths with particularly good dispersion characteristics are obtained if such baths are modified with small amounts of high molecular weight amines as dispersing agents, preferably alkyl amines with 8 to 32 carbon atoms in the molecule, in addition to being modified with the customary cleansing intensifiers, such as high-molecular weight alkyl sulfates, alkyl sulfonates and alkyl benzene sulfonates, ethylene oxide addition products of high molecular weight fatty alcohols and fatty acids, high molecular weight acid amides, amines or mercaptans, as well as other known anionic, cationic or non-ionic surface-active substances.

The alkyl radicals of the high molecular weight amines used in accordance with my invention may be interrupted by heteroatoms, such as nitrogen, oxygen or sulfur, and/ or may be substituted by amino-, iminoor hydroxylgroups. Compounds of this type are, for example, octyl amine, decyl amine, dodecyl amine, hexadecyl amine, primary amine mixtures, such as those which are obtained by reduction of naturally-occurring fatty acid mixtures and subsequent amination thereof, for example, amine mixtures which are derived from coconut fatty acids or tallow fatty acids. Also included are secondary amines, such as dodecyl-oxyethyl amine, hexadecyl-methyl amine,

dihexadecyl amine, tertiary amines, such as dodecyl-di ethyl amine, octadecyl-diethyl amine, as well as amines the aliphatic hydrocarbon radicals of which are interrupted by heteroatoms, such as B-aminoethyl-decyl ether, {3 aminoethyl dodecyl thioether, dodecylamino-ethyl amine and the like. Furthermore, such non-aliphatic amines as naphthenyl amine, abietyl amine, cyclohexyl amine or alkyl-cyclohexyl amine may be used.

An essential characteristic of my invention is that the high molecular weight alkyl amines are primarily used in the form of free bases. If technical amines or amine mixtures which in some cases contain ammonia from the manufacturing process are used, the undesirable, strong alkalinity may be buffered by adding less than stoichiometric amounts (based on the amine) of carboxylic acids. However, too high a degree of neutralization may decrease the dispersing capability to a substantial extent.

The addition of the high molecular weight amines is accomplished in the customary fashion by adding to the cleaning bath amounts of 0.1 to 10.0 gm., preferably 0.1 to 2.0 gm., per liter of cleaning bath, the amounts within certain limits being dependent upon the amount of water to be dispersed. In general, the amount of water in the dry-cleaning bath should not exceed 1% of the total amount of liquid.

The alkyl amines may be added to all customary drycleaning baths. Suitable dry-cleaning agents include, for example, gasoline, ligroin and other low-boiling-point parafiin hydrocarbons and mixtures thereof; benzene, toluene, xylene and other low-boiling-point aromatic hydrocarbons or mixtures thereof; as well as chlorinated hydrocarbons, such as carbon tetrachloride, trichloroethylene, perchloro-ethylene and mixtures thereof. The drycleaning baths may be used for all customary purposes, i.e., for cleaning textiles, feathers, pillow material, filler material and the like.

It is well known that the water-dispersing capability of cleansing intensifiers can be increased by the addition of high molecular weight fatty alcohols, ethyoxylated products of high molecular weight fatty alcohols, carboxylic acids or acid amides, or similar products. However, it is surprising that the high molecular weight amines, especially the alkyl amines, exhibit a far better waterdispersing capability in dry-cleaning baths in comparison to the known additives, and that dry-cleaning baths modified with the amine additives are also marked by a substantially better filterability.

My invention is further illustrated below by the following series of tests which have been carried out to illustrate the effectiveness of the cleansing intensifier of my invention to prepare stable dispersion mixtures as compared with well known compounds of the prior art. It will be understood that the specific bath compositions are solely for the purpose of illustrating my invention and that I do not intend to be limited thereby.

TEST ARRANGEMENT The dispersion stability of mixtures which consisted of perchloroethylene modified with 5 gm./ liter of a cleansing intensifier and 10 00. per liter of water, and to which varying amounts of different dispersing agents had been added, was tested in a shaking cylinder. The mixtures were vigorously shaken for three minutes with a shaking machine, and thereafter the time which elapsed until the first indication of a phase separation was measured. In this manner the varying effectiveness of the respective dispersing agents was visualized.

The test results with three commercial cleansing intensifiers are summarized in Tables 1 to 3 below. At the beginning of each of these tables the control Value without a dispersing agent additive is indicated and under this control value the values with known dispersing agents are listed under A, and the values with dispersing agents according to the invention are listed under B.

TABLE 1 Perchlol'octhylcne With Gin/Liter Dodecyl-Benzene Sodium Sulfonate and cc./Liter Water Time to first phase separation in seconds Dispersing agent None 2 gm./liter addition product of 2 mols ethylene oxide with an unsaturated fatty alcohol mixture having a carbon chain length of 16 to 18 carbon atoms 2 gin/liter addition product of 5 mols ethylene ox de with an unsaturated fatty alcohol mixture having a carbon chain length of 16 to 18 carbon atoms"- 2 gnL/liter palmitic acid plus 0.6 gin/liter mono ethanol amine 2 2 gm./liter addition product of 3 mols ethylene oxide with stearic acid amide 2 ure derived from tallow fatty acids plus 0.4 gm./ ter acetic acid 55 2 gm./liter amine mixture derived from tallow fatty acids plus 1.2 gm./liter lauric acid 85 TABLE 2 Perchloroethylcne With 5 Gin/Liter of the Ammonium Salt of Acid Dodecyl-Sulfuric Acid Ester and 10 can/Liter of Water Time to first phase Dispersing agent: separation in seconds None 1 2 gmJliter addition product of 2 mols ethylene oxide with an unsaturated fatty alcohol mixture having a carbon chain length of 16 to 18 carbon atoms 1 2 gm./liter addition product of 5 mols ethylene oxide with an unsaturated fatty alcohol mixture having a carbon chain length of 16 to 18 carbon aton1s l 2 gm./liter palmitic acid plus 0.6 gin/liter monoethanol amine 1 2 g1n./1iter addition product of 3 mols ethylene oxide with stearic acid amide 8 2 gm./liter amine mixture derived from tallow fatty acids 90 2 gull/liter dodecyl-diethyl amine 7O 2 gm./liter fi-aminoethyl-dodecylthioether 55 2 gm./litcr amine mixture derived from tallow fatty acids plus 0.5 gn1./liter lauric acid 85 2 gin/liter N-tetrahydrofurfuryl-N-octadec la ine 45 2 gm./liter naphthenyl-cyclohexylamine 41 TABLE 3 2 gm./liter addition product of 2 mols ethylene oxide with an unsaturated fatty alcohol mixture having a carbon chain length of 16 to 18 carbon atoms 5 2 gm./liter addition product of 5 mols ethylene oxide with an unsaturated fatty alcohol mixture having a carbon chain length of 16 to 18 carbon atoms 5 2 gm./liter amine mixture derived from tallow fatty 2 a s 0.8 gm./liter amine mixture derived from tallow fatty acids plus 0.4 gm./liter palmitic acid 38 2 gin/liter amine mixture derived from tallow fatty acids plus 0.4 gm./liter acetic acid 12 When, instead of the perchloroethylene in the above examples, a higher gasoline fraction was used as the solvent, similar values were obtained.

While I have set forth a number of specific embodiments of my invention, it will be understood that these 4 are solely for the purpose of illustration and comparison, and that various changes and modifications may be made in the invention without departing from the spirit of the invention or the scope of the following claims.

I claim:

1. A process for drycleaning fibrous materials which comprises cleaning said fibrous materials in a dry-cleaning bath comprising a dry-cleaning solvent, a quantity of water not greater than 1%, and 0.1 to 10 gn1./liter of high molecular weight alkyl monoamines having from 8 to 32 carbon atoms in the molecule, said alkyl monoamines being selected from the group consisting of those with at least one alkyl radical having at least 8 carbon atoms, derivatives thereof wherein the alkyl radicals are interrupted by hetero-atoms selected from the group consisting of oxygen, nitrogen and sulfur, and derivatives thereof wherein the alkyl radicals are substituted by groups selected from the group consisting of amino, imino and hydroxyl groups, in the form of their free bases.

2. The process of claim 1, wherein a carboxylic acid is added to the bath, said carboxylic acid being added in less than stoichiometric amounts based on the amine.

3. A process for dry-cleaning fibrous materials which comprises cleaning said fibrous materials in a dry-cleaning bath comprising a dry-cleaning solvent, a quantity of water not greater than 1%, cleansing intensifiers selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, ethylene oxide addition products of high molecular weight fatty alcohols and fatty acids, and high molecular weight acid amides, amines and mercaptans, and 0.1 to 10 gm./liter of high molecular weight alkyl monoamines having from 8 to 32 carbon atoms in the molecule, said alkyl monoamines being selected from the group consisting of those with at least one alkyl radical having at least 8 carbon atoms, derivatives thereof wherein the alkyl radicals are interrupted by hetero-atoms selected from the group consisting of oxygen, nitrogen and sulfur, and derivatives thereof wherein the alkyl radicals are substituted by groups selected from the group consisting of amino, imino and hydroxyl groups, in the form of their free bases.

4. A method for forming a dry-cleaning bath effective against both water-soluble and water-insoluble soil which comprises adding to a dry-cleaning solvent not greater than about 1% water, and 0.1 to 10 gm./liter of high molecular weight alkyl monoamines having from 8 to 32 carbon atoms in the molecule, said alkyl monoamines being selected from the group consisting of those with at least one alkyl radical having at least 8 carbon atoms, derivatives thereof wherein the alkyl radicals are interrupted by hetero-atoms selected from the group consisting of oxygen, nitrogen and sulfur, and derivatives thereof wherein the alkyl radicals are substituted by groups selected from the group consisting of amino, imino and hydroxyl groups, in the form of their free bases.

5. A method for forming a dry-cleaning bath effective against both water-soluble and water-insoluble soil which comprises adding to a dry-cleaning solvent not greater than about 1% water, cleansing intensifiers selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, ethylene oxide addition products of high molecular Weight fatty alcohols and fatty acids and high molecular weight acid amides, amines and mercaptans, and 0.1 to 10 gm./liter of high molecular weight alkyl monoamines having from 8 to 32 carbon atoms in the molecule, with at least one alkyl radical having at least 8 carbon atoms, wherein the alkyl radicals of said high molecular weight amines may be interrupted by hetero-atoms selected from the group consisting of oxygen, nitrogen and sulfur and substituted by groups selected from the group consisting of amino, imino and hydroxyl groups, in the form of their free bases.

6. The method of claim 6 wherein a carboxylic acid is added to the bath, said carboxylic acid being added in less than stoichiometric amounts based on the amine.

7. A dry-cleaning bath for cleaning fibrous materials containing some water-soluble soil which comprises a dry-cleaning solvent, not greater than about 1% water, and 0.1 to g m./liter of high molecular weight alkyl monoamines having from 8 to 32 carbon atoms in the molecule, said alkyl monoamines being selected from the group consisting of those with at least one alkyl radical having at least 8 carbon atoms, derivatives thereof wherein the alkyl radicals are interrupted by hetero-atoms selected from the group consisting of oxygen, nitrogen and sulfur, and derivatives thereof wherein the alkyl radicals are substituted by groups selected from the group consisting of amino, imino and hydroxyl groups, in the form of their free bases.

8. A dry-cleaning bath for cleaning fibrous materials containing some water-soluble soil which comprises a dry-cleaning solvent, not greater than about 1% of water, cleansing intensifiers selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, ethylene oxide addition products of high molecular weight fatty alcohols and fatty acids, and high molecular Weight acid amides, amines and mercaptans, and 0.1 to 10 gm./ liter of high molecular weight alkyl monoamines having from 8 to 32 carbon atoms in the molecule, said alkyl monoamines being selected from the group consisting of those with at least one alkyl radical having at least. 8 carbon atoms, derivatives thereof wherein the alkyl radicals are interrupted by heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, and derivatives thereof wherein the alkyl radicals are substituted by groups selected from the group consisting of amino, imino and hydroxyl groups, in the form of their free bases.

9. The bath of claim 8 wherein a carboxylic acid is added to the bath, said carboxylic acid being added in less than stoichiometric amounts based on the amine.

10. The bath of claim 8 wherein the dry-cleaning agent is a higher gasoline fraction.

11. The bath of claim 8 wherein the dry-cleaning agent is perchloroethylene.

12. The bath of claim 11 wherein the amine is hexadecyl amine.

13. The bath of claim 11 wherein the amine is dodecyl ethyl amine.

14. The bath of claim 11 wherein the amine is 5- aminoethyl-decyl ether.

15. The bath of claim 11 wherein the amine is dihexadecyl amine.

16. The bath of claim 11 wherein the amine is dodecyl oxyethyl amine.

17. The bath of claim 11 wherein the amine is dodecylamino-ethyl amine.

18. The bath of claim 11 wherein the amine is dodecyl diethyl amine.

19. The bath of claim 11 wherein the amine is B- aminoethyl-dodecyl-thioether.

20. The bath of claim 11 wherein the amine is a mixture of amines derived from tallow fatty acids.

References Cited in the file of this patent UNITED STATES PATENTS 1,911,289 Reddish May 30, 1933 2,052,891 Merrill Sept. 1, 1936 2,267,205 Kyrides Dec. 23, 1941 2,334,517 Tucker Nov. 16, 1943 2,271,635 Flett Feb. 3, 1952 

3. A PROCESS FOR DRY-CLEANING FIBROUS MATERIALS WHICH COMPRISES CLEANING AND FIBROUS MATERIALS IN A DRY-CLEANING BATH COMPRISING A DRY-CLEANING SOLVENT, A QUANTITY OF WATER NOT GREATER THAN 1%, CLENSING INTENSIFIERS SELECTED FROM THE GROUP CONSISTING OF ALKYL SULFATES, ALKYL SULFONATES, ALKYL BENZENE SULFONATES, ETHYLENE OXIDE ADDITION PRODUCTS OF HIGH MOLECULE WEIGHT FATTY ALCOHOLS AND FATTY ACIDS, AND HIGH MOLECULAR WEIGHT ACID AMIDES, AMINES AND MERCAPTANS, AND 0.1 TO 10 GM./LITER OF HIGH MOLECULAR WEIGHT ALKYL MONOAMINES HAVING FROM 8 TO 32 CARBON ATOMS IN THE MOLECULE, SAID ALKYL MONOAMINES BEING SELECTED FROM THE GROUP CONSISTING OF THOSE WITH AT LEAST ONE ALKYL RADICAL HAVING AT LEAST 8 CARBON ATOMS, DERIVATIVES THEREOF WHEREIN THE ALKYL RADICALS ARE INTERRUPTED BY HETERO-ATOMS SELECTED FROM THE GROUP CONSISTING OF OXYGEN, NITROGEN AND SULFUR, AND DERIVATIVES THEREOF WHEREIN THE ALKYL RADICALS ARE SUBSTITUTED BY GROUPS SELECTED FROM THE GROUP CONSISTING OF AMINO, IMINO AND HYDROXYL GROUPS, IN THE FORM OF THEIR FREE BASES. 